Radiation-curable composite layered sheet or film

ABSTRACT

A radiation-curable composite layered sheet or film comprising at least one substrate layer and one outer layer, said outer layer being composed of a radiation-curable composition having a glass transition temperature of more than 40° C.

The invention relates to a radiation-curable composite layered sheet orfilm comprising at least one substrate layer and one outer layer, saidouter layer being composed of a radiation-curable composition having aglass transition temperature of more than 40° C.

The specification further relates to a process for producing theradiation-curable composite layered sheet or film and to a process forproducing moldings coated with said sheet or film.

DE-A-196 28 966 and DE-A-196 54 918 disclose dry-paint films where thepaint has a glass transition temperature of less than 40° C. Curingrequires two steps: a partial cure before the film is adhesively bondedto substrates, and the final cure thereafter.

EP-A-361 351 likewise discloses a dry-paint film. Here, the film isradiation-cured before being applied to the substrate moldings.

DE-A-196 51 350 (O.Z. 47587) describes composite layered sheets andfilms which consist of thermoplastic materials and do not have aradiation-curable coating.

A disadvantage of the radiation-curable dry-paint films known to date isthat two or more steps are frequently required to effect the radiationcure, as described in DE-A-196 28 966. Where the film is fullyradiation-cured prior to the coating operation, it often becomes brittleand difficult to deform, which is deleterious to its further processing.

With existing radiation-curable films, the coated moldings often lacksufficient scratch resistance and sufficient elasticity when worked onmechanically. It is an object of the present invention to provideradiation-curable composite layered sheets or films which are easy toprocess and which lend themselves to the coating of moldings byextremely simple techniques. The coated moldings are to have goodmechanical properties, effective resistance to external influences, suchas a good weathering stability, for example, and in particular are to bemechanically stable—having, for example, good scratch resistance andhigh elasticity.

We have found that this object is achieved by the radiation-curablecomposite layered sheet or film defined at the outset and referred tofor short as film hereinafter. We have also found processes for coatingmoldings with the film, and the coated moldings.

The film must include a substrate layer and an outer layer which isapplied to the substrate layer directly or, where there are furtherinterlayers, indirectly.

Outer Layer

The outer layer is radiation-curable. Accordingly, the outer layercomposition used is radiation-curable and comprises groups curable by afree-radical or ionic mechanism (curable groups for short). Preferenceis given to free-radically curable groups.

The radiation-curable composition is preferably transparent. Aftercuring has been accomplished, as well, the outer layer is preferablytransparent: that is, it is a clearcoat layer.

A key constituent of the radiation-curable compositions is the binder,which by filming forms the outer layer.

The radiation-curable composition preferably comprises a binder selectedfrom

-   i) polymers containing ethylenically unsaturated groups-   ii) mixtures of i) with ethylenically unsaturated compounds of low    molecular mass-   iii)mixtures of saturated thermoplastic polymers with ethylenically    unsaturated compounds.-   i)

Examples of suitable polymers include those of ethylenically unsaturatedcompounds, but also polyesters, polyethers, polycarbonates, polyepoxidesor polyurethanes.

They suitably include unsaturated polyester resins, which consistessentially of polyols, especially diols, and polycarboxylic acid,especially dicarboxylic acid, where one of the esterification componentscontains a copolymerizable, ethylenically unsaturated group. Examples ofthe components in question include maleic acid, fumaric acid, and maleicanhydride.

Preference is given to polymers of ethylenically unsaturated compounds,such as are obtained in particular by means of free-radical additionpolymerization

The free-radical addition polymers include, in particular, polymerscomposed of more than 40% by weight, with particular preference morethan 60% by weight, of acrylic monomers, particularly C₁-C₈, preferablyC₁-C₄, alkyl (meth)acrylates. By way of ethylenically unsaturatedgroups, the polymers include in particular (meth)acrylic groups. Thesegroups may be attached to the polymer by, for example, reacting(meth)acrylic acid with epoxide groups in the polymer (e.g., by usingglycidyl (meth)acrylate as a comonomer).

Preference is likewise given to polyurethanes. Their unsaturated groupsare again preferably (meth)acrylic groups, attached to the polyurethaneby reacting hydroxyalkyl (meth)acrylates with isocyanate groups, forexample.

The polymers i) per se can be processed as thermoplastics.

-   ii)

The unsaturated polymers i) may also be used in mixtures withethylenically unsaturated compounds of low molecular mass.

Low molecular mass compounds in this context are compounds having anumber average molecular weight of less than 2000 g/mol (as determinedby gel permeation chromatography using a polystyrene standard).

Suitable examples include free-radically polymerizable compoundscontaining only one ethylenically unsaturated, copolymerizable group.

By way of example, mention may be made of C₁-C₂₀ alkyl (meth)acrylates,vinylaromatics having up to 20 carbon atoms, vinyl esters of carboxylicacids containing up to 20 carbon atoms, ethylenically unsaturatednitrites, vinyl ethers of alcohols containing from 1 to 10 carbon atoms,and aliphatic hydrocarbons having from 2 to 20, preferably from 2 to 8,carbon atoms and 1 or 2 double bonds.

Preferred alkyl (meth)acrylates are those with a C₁-C₁₀ alkyl radical,such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethylacrylate and 2-ethylhexyl acrylate.

Also suitable, in particular, are mixtures of the alkyl (meth)acrylates.

Examples of vinyl esters of carboxylic acids having from 1 to 20 carbonatoms are vinyl laurate, vinyl stearate, vinyl propionate, and vinylacetate.

Examples of suitable vinylaromatic compounds are vinyltoluene,α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, and preferablystyrene.

Examples of nitriles are acrylonitrile and methacrylonitrile.

Examples of suitable vinyl ethers are vinyl methyl ether, vinyl isobutylether, vinyl hexyl ether, and vinyl octyl ether.

As nonaromatic hydrocarbons having from 2 to 20, preferably from 2 to 8,carbon atoms and one or two olefinic double bonds, mention may be madeof butadiene, isoprene, and also ethylene, propylene, and isobutylene.

Compounds contemplated include preferably free-radically polymerizablecompounds containing two or more ethylenically unsaturated groups.

The compounds in question are particularly (meth)acrylate compounds,with preference being given in each case to the acrylate compounds:i.e., the derivatives of acrylic acid.

Preferred (meth)acrylate compounds contain from 2 to 20, more preferablyfrom 2 to 10, and with very particular preference from 2 to 6,copolymerizable, ethylenically unsaturated double bonds.

As (meth)acrylate compounds mention may be made of (meth)acrylates andin particular acrylates of polyfunctional alcohols, especially thosewhich contain no functional groups other than the hydroxyl groups or, ifhaving further functional groups, contain only ether groups. Examples ofsuch alcohols include difunctional alcohols, such as ethylene glycol andpropylene glycol, and their higher condensation analogs, such asdiethylene glycol, triethylene glycol, dipropylene glycol, tripropyleneglycol, etc., butanediol, pentanediol, hexanediol, neopentyl glycol,alkoxylated phenolic compounds, such as ethoxylated and/or propoxylatedbisphenols, cyclohexanedimethanol, alcohols with a functionality ofthree or more, such as glycerol, trimethylolpropane, butanetriol,trimethylolethane, pentaerythritol, dimethylolpropane,dipentaerythritol, sorbitol, mannitol, and the corresponding alkoxylatedalcohols, especially ethoxylated and propoxylated alcohols.

The alkoxylation products are obtainable conventionally by reacting theabove alcohols with alkylene oxides, especially ethylene oxide orpropylene oxide. With preference the degree of alkoxylation per hydroxylgroup is from 0 to 10, i.e., 1 mol of hydroxyl group may be alkoxylatedpreferably with up to 10 mol of alkylene oxides.

(Meth)acrylate compounds further include polyester (meth)acrylates,which are the (meth)acrylic esters of polyesterols.

Examples of suitable polyesterols are those such as may be prepared byesterifying polycarboxylic acids, preferably dicarboxylic acids, withpolyols, preferably diols. The starting materials for suchhydroxyl-containing polyesters are known to the skilled worker. Asdicarboxylic acids preferential use may be made of succinic acid,glutaric acid, adipic acid, sebacic acid, o-phthalic acid, their isomersand hydrogenation products, and also esterifiable derivatives, such asanhydrides or dialkyl esters of said acids. Suitable polyols include theabovementioned alcohols, preferably ethylene glycol, 1,2- and1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol,and cyclohexanedimethanol, and also polyglycols of the ethylene glycoland propylene glycol types.

Polyester (meth)acrylates may be prepared in a plurality of stages orelse in a single stage, as described, for example, in EP 279 303, fromacrylic acid, polycarboxylic acid, and polyol.

-   iii)

Examples of suitable saturated thermoplastic polymers include polymethylmethacrylate, polystyrene, high-impact polymethyl methacrylate,high-impact polystyrene, polycarbonate and polyurethanes.

Radiation-curability is ensured by adding an ethylenically unsaturated,radiation-curable compound. This may be one of the compounds listedunder i) and/or ii).

A key feature of the binder i) to iii) is that its glass transitiontemperature (Tg) is more than 40° C., preferably more than 50° C., andwith particular preference more than 60° C. In general, the Tg will notexceed a level of 130° C. (The Figures relate to the binder beforeradiation curing.)

The glass transition temperature, Tg, of the binder may be determined bythe DSC (differential scanning calorimetry) method in accordance withASTM 3418/82.

The amount of the curable groups, i.e., the ethylenically unsaturatedgroups, is preferably from 0.001 to 0.2 mol, with particular preferencefrom 0.005 to 0.15 mol, with very particular preference from 0.01 to 0.1mol, per 100 g of binder (solids; that is, without water or othersolvents).

The binder preferably has a viscosity of from 0.02 to 100 Pas at 140° C.(as determined in a rotational viscometer).

The radiation-curable compositions may include further constituents.Particular mention may be made of photoinitiators, leveling agents, andstabilizers. For outdoor use, i.e., for coatings directly exposed todaylight, the compositions will particularly include UV absorbers andfree-radical scavengers.

UV absorbers convert UV radiation into heat energy. Known UV absorbersinclude hydroxybenzophenones, benzotriazoles, cinnamic esters, andoxalanilides.

Free-radical scavengers bind free-radical intermediates that are formed.Major free-radical scavengers include sterically hindered amines, knownas HALS (hindered amine light stabilizers).

For outdoor applications, the overall UV absorber and free-radicalscavenger content is preferably from 0.1 to 5 parts by weight, withparticular preference from 0.5 to 4 parts by weight, based on 100 partsby weight of the radiation-curable compounds.

Moreover, besides radiation-curable compounds, the radiation-curablecomposition may further include compounds which contribute to curing byother chemical reactions. Suitable examples include polyisocyanates,which crosslink with hydroxyl or amino groups.

The radiation-curable composition may be in water-free and solvent-freeform, or in the form of a solution or dispersion.

Preference is given to water- and solvent-free radiation-curablecompositions, or aqueous solutions or aqueous dispersions.

Particular preference is given to water- and solvent-freeradiation-curable compositions.

The radiation-curable composition is thermoplastically deformable and inparticular may be extruded.

The above radiation-curable compositions form the outer layer. The layerthickness (after drying and curing) is preferably from 10 to 100 μp.

Substrate layer

The substrate layer serves as a support and is intended to ensure thatthe composite as a whole remains permanently tough.

The substrate layer consists preferably of a thermoplastic polymer,particularly polymethyl methacrylates, polybutyl methacrylates,polyurethanes, polyethylene terephthalates, polybutylene terephthalates,polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins,polyamides, polycarbonates (PC), acrylonitrile-butadiene-styrene (ABS)polymers, acrylic-styrene-acrylonitrile (ASA) copolymers,acrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM),polyether imides, polyether ketones, polyphenylene sulfides,polyphenylene ethers or mixtures thereof.

Preference is given to ASA, especially in accordance with DE 19 651 350,and to the ASA/PC blend. Preference is likewise given to polymethylmethacrylate (PMMA) or impact-modified PMMA.

The layer thickness is preferably from 50 μm up to 5 mm. Particularpreference, especially when the substrate layer is injection-backmolded,is given to thicknesses of from 100 to 1000 μm, in particular from 100to 500 μm.

The polymer of the substrate layer may comprise additives, especiallyfillers or fibers. The substrate layer may also be colored, in whichcase it may also act as a coloring layer.

Further layers

The film may include further layers in addition to the outer layer andthe substrate layer.

Suitable examples include coloring interlayers or further layers ofthermoplastic material (thermoplastic interlayers), which strengthen thefilm or serve as release layers.

Thermoplastic interlayers may be made of the polymers listed above underSubstrate layer.

Particular preference is given to polymethyl methacrylate (PMMA),preferably impact-modified PMMA. Mention may also be made ofpolyurethane. Coloring layers may likewise consist of said polymers.They include dyes or pigments which are distributed in the polymerlayer.

One preferred film has, for example, the following layer structure, thealphabetical sequence corresponding to the spatial disposition:

-   A) outer layer-   B) thermoplastic interlayer (optional)-   C) coloring interlayer (optional)-   D) substrate layer-   E) adhesive layer (optional)

On the reverse side (reverse for short) of the substrate layer (i.e.,the side facing the article to be coated) there may have been applied anadhesive layer, where the film is to be bonded adhesively to thesubstrate.

Applied to the transparent outer layer there may be a protective layer,e.g., a removable film, which prevents unintended curing. Its thicknessmay amount, for example, to from 50 to 100 μm. The protective layer maybe composed, for example, of polyethylene or polyterephthalate. Theprotective layer may be removed prior to irradiation.

Alternatively, irradiation may take place through the protective layer;for this, the protective layer must be transparent in the irradiationwavelength range.

The overall thickness of the film is preferably from 50 to 1000 μm.

Production of the Composite Sheet or Film

The production of a composite from the layers B) to D) may take place,for example, by coextrusion of all or some of the layers.

For coextrusion, the individual components are fluidified in extrudersand, using special means, are contacted with one another in such a wayas to give the films having the layer sequence described above. Forexample, the components may be coextruded through a slot die. Thisprocess is elucidated in EP-A2-0 225 500. As a supplement to theprocesses described herein, it is also possible to use the process knownas adapter coextrusion.

The composite may be produced by conventional processes, for example, bycoextrusion, as described above, or by lamination of the layers, in aheatable nip, for example. In this way it is possible first of all theproduce a composite of the layers except for the outer layer, and thento apply the outer layer by conventional techniques.

The radiation-curable composition may be applied to the substrate layeror the composite in a simple way, by casting, rolling, knife coating,spraying, etc., for example, and dried where appropriate.

Preference is given to extruding the radiation-curable composition,i.e., the outer layer. Where appropriate, the radiation-curablecomposition may also be coextruded with one or more further layers.

In the case of extrusion (including coextrusion) of theradiation-curable compositions, the preparation of the radiation-curablecomposition by mixing of its constituents, and the preparation of theouter layer, may take place in one operation.

To this end, thermoplastic constituents, e.g., unsaturated polymers i)or saturated polymers iii) (see above), may first of all be melted inthe extruder. The requisite melting temperature depends on the polymerin question. After the melting operation, preferably, the furtherconstituents may be metered in, especially radiation-curable compoundsii) of low molecular mass (see above). The compounds act asplasticizers, thereby reducing the temperature at which the compositionis in melt form. The temperature on addition of the radiation-curablecompound must lie in particular below a critical temperature at whichthe radiation-curable compound undergoes thermal curing.

The critical temperature may easily be determined by means of acalorimetric measurement, i.e., a measurement of the heat absorbed withincreasing temperature, in accordance with the above-describeddetermination of the glass transition temperature.

The radiation-curable composition is then extruded directly as the outerlayer onto the existing composite or, in the case of coextrusion, isextruded with layers of the composite. Extrusion leads directly to thecomposite layered sheet or film.

The outer layer is blocking-resistant, i.e., does not adhere, and isradiation-crosslinkable. The composite sheet or film isthermoelastically deformable. If desired, a protective layer (protectivefilm) may be laid down on the outer layer directly following productionof the composite sheet or film.

The composite layered sheet or film possesses high gloss and goodmechanical properties. Rarely is cracking observed.

The extensibility of the composite layered sheet or film is preferablyat least 100%, relative to the unextended state (at 140° C., with athickness of 30 μm).

Use Processes

The film may be stored without partial curing (as described in DE-A-19628 966) until subsequent use.

There is very little, if any, sticking or deterioration in performanceproperties observed up until the time of subsequent use.

The film is used preferably as a coating material.

In this case, a preferred procedure is first to coat the substrates andthen to cure the outer layer by means of radiation.

Coating may take place by bonding the film to the substrates. For thispurpose, on the reverse of the substrate layer, the film is preferablyprovided with the adhesive layer E. Suitable substrates include those ofwood, plastic or metal.

Coating may also take place by injection backmolding of the film. Forthis purpose the film is thermoformed, preferably in a thermoformingmold, and the reverse of the substrate layer is injection-backmoldedwith polymer composition. The polymer composition comprises, forexample, polymers which were listed above in the description of thesubstrate layer or, for example, polyurethane, especially polyurethanefoam. The polymers may comprise additives, particular examples includingfibers, such as glass fibers, or fillers.

The radiation curing of the outer layer takes place in this casepreferably after the thermoforming operation and with particularpreference after the injection backmolding of the film.

The radiation cure is effected with high-energy light, e.g., UV light,or electron beams. It may take place at relatively high temperatures.Preference is given here to a temperature above the Tg of theradiation-curable binder.

Where crosslinkers which bring about additional thermal crosslinking,such as isocyanates, have been included too, it is possible to carry outthermal crosslinking by raising the temperature to up to 150° C.,preferably up to 130° C., which can be done, for example, simultaneouslywith or else subsequent to radiation curing.

Applications and Advantages

The films may be used to coat shaped articles. Any desired shapedarticles are amenable. With particular preference, the films are used tocoat shaped articles where very good surface properties, high weatheringstability, and good UV resistance are important. The resulting surfacesare, moreover, highly scratch-resistant and firmly adhering, therebyreliably preventing destruction of the surfaces by scratching ordelamination of the surfaces. Accordingly, shaped articles for useoutdoors, outside of buildings, constitute a preferred area ofapplication. In particular, the films are used to coat motor vehicleparts, with suitable examples including wings, door trim components,fenders, spoilers, skirts, and exterior mirrors.

EXAMPLES

I Synthesis of a Radiation-curable Coating Material: 426.2 g ofisopropylidenedicyclohexanol were dispersed roughly in 566.3 g ofhydroxyethyl acrylate at 60° C. with stirring. To this dispersion therewere added 1695.2 g of an isocyanurate of hexamethylene diisocyanate,1.34 g of hydroquinone monomethyl ether, 2.69 g of1,6-di-tert-butyl-para-cresol and 0.134 g of phenothiazine. Followingthe addition of 0.538 g of dibutyltin dilaurate, the batch heated up to93° C. over the course of 20 minutes. After it had been cooled to 75°C., 300 g of acetone were metered in. When the NCO value had dropped to0.66%, a further 370 g of acetone were added, followed by dropwiseaddition of 14.87 g of methanol. The mixture was then stirred at 60° C.until the NCO value had fallen to 0. The resin was admixed with anappropriate photoinitiator, applied to a Luran S 797 injectionbackmolding film, and exposed at 100° C. The pencil hardness of thefilms was determined in accordance with ASTM D 3363.

Pencil hardness of the coated film: 2H

Comparison: pencil hardness of the untreated injection backmolding film(Luran S 797): B

Comparison: pencil hardness of the injection-backmolding protection film(Lucryl G 87): softer than 6B

Two uncured acrylated polyacrylates having different Tg values, and theuncured urethane acrylate, were applied to a Luran S support film andthermoformed at an elevated temperature. After thermoforming, the filmswere exposed at 100° C.

Hardness of the Films: Urethane acrylate 2H Binder resin (Tg (beforeexposure) = 46° C.) 3H Binder resin (Tg (before exposure) = −6° C.) HII Production of a Radiation-curable Outer Layer

-   -   IIa

First of all, a photoactive mixture was prepared by mixing the followingconstituents: % by Material weight chemical composition Ebecryl ® 40 23Alkoxylated pentaerythritol triacrylate (UCB) Ebecryl ® IRR 264 41Triacrylate of a tris(2-hydroxyethyl) isocyanurate (UCB) Ebecryl ® 129011 Aliphatic urethane acrylate (UCB) Ebecryl ® 5129 11 Aliphaticurethane acrylate (UCB) Ebecryl ® 350 5 Silicone diacrylate (UCB)Tinuvin ® 292 1 HALS additive (Ciba SC) Tinuvin ® 400 1 UV absorber(Ciba SC) Irgacure ® 184 6 Photoinitiator (Ciba SC) Lucirin ® TPO 1Photoinitiator (BASF)

-   -   The polymethyl methacrylate (PMMA) Lucryl® G 55 was melted at        from 190 to 220° C. in an extruder and the photoactive mixture        (one part by weight of the mixture to three parts by weight of        Lucryl) was metered into the melt at below 170° C. The resulting        melt was extruded in the form of a radiation-curable film.    -   The film obtained was blocking-resistant (i.e., nonadhering) and        the resulting composite film was deformable and thermoformable.        The radiation-curable outer layer was cured using UV light. (120        W/cm, belt speed 2 to 3 m/min).    -   IIb

The photoactive mixture consisted of: % by Material weight chemicalmixture Ebecryl 2000 43 Aliphatic urethane acrylate (UCB) Ebecryl 264 22Aliphatic triacrylate of a urethane acrylate in HDDA (UCB) Lucirin TPO-L1 Photoinitiator (BASF) CGI 184 5 Photoinitiator (Ciba SC) Tinuvin 292 2HALS additive (Ciba SC) Tinuvin 400 2 UV absorber (Ciba SC) SR 9003 7Propoxylated neopentyl glycol diacrylate (Cray Valley) Ebecryl 350 2Silicone diacrylate (UCB) CN 965 10 Aliphatic UR-Ac (Cray Valley) SR 3445 Polyethylene glycol diacrylate (Cray Valley)

-   -   The polyurethane KU-1-8602 (Bayer) was melted at 180 to 220° C.        in an extruder and the photoactive mixture (one part by weight        to three parts by weight of polyurethane) was metered into the        melt at 160° C. The resulting melt was extruded in the form of a        radiation-curable film.    -   The resulting outer layer was blocking-resistant, and the        resulting film was deformable and thermoformable.    -   The radiation-curable outer layer was cured using UV light (120        W/cm, belt speed 2 to 3 m/min).

1-13. (canceled)
 14. A radiation-curable, composite layered sheet orfilm comprising at least one substrate layer, one outer layer, and acoloring interlayer between the at least one substrate layer and theouter layer, wherein the at least one substrate layer comprises athermoplastic polymer selected from the group consisting of polymethylmethacrylates, polybutyl methacrylates, polyethylene terephthalates,polybutylene terephthalates, polyvinylidene fluorides, polyvinylchlorides, polyolefins, polyamides, polycarbonates,acrylonitrile-butadiene-styrene (ABS) polymers,acrylic-styrene-acrylonitrile (ASA) copolymers,acrylonitrile-ethylene-propylene-diene-styrene copolymers (A-EPDM),polyether imides, polyether ketones, polyphenylene sulfides,polyphenylene ethers and mixtures thereof, wherein the outer layercomprises a radiation-curable composition comprising a binder having aglass transition temperature of more than 40° C., and wherein the binderis a polyurethane obtained by a reaction comprising reactinghydroxylalkyl (meth)acrylic groups with isocyanate groups.
 15. A methodof making a radiation-curable composite layered sheet or film, themethod comprising applying a radiation-curable composition comprising abinder having a glass transition temperature of more than 40° C.; andproducing the film or sheet of claim
 14. 16. The sheet or film asclaimed in claim 14, further comprising an adhesive layer in contactwith the at least one substrate layer opposite the coloring interlayer.17. A method of making a radiation-curable composite layered sheet orfilm, the method comprising applying one outer layer on at least onesubstrate layer and a coloring interlayer, to make the sheet or film,wherein the coloring interlayer is between the at least one substratelayer and the one outer layer, wherein the outer layer during theapplying comprises a water-free and solvent-free radiation-curablecomposition comprising a binder having a glass transition temperature ofmore the 40° C., and wherein the binder is obtained by a reactioncomprising reacting hydroxylalkyl (meth)acrylic groups with isocyanategroups.
 18. The sheet or film of claim 14, wherein the applying isperformed by a method selected from the group consisting of casting,rolling, knife-coating, spraying, extruding, co-extruding, andcombinations thereof.
 19. The sheet or film of claim 14, wherein thebinder is a thermoplastic polymer.
 20. The sheet or film of claim 14,wherein the glass transition temperature of the binder is from 40 to130° C.
 21. The sheet or film of claim 14, wherein the binder has aviscosity of from 0.02 to 100 Pas at 140° C. determined by a rotationalviscometer.
 22. The sheet or film of claim 14, wherein the bindercomprises from 0.001 to 0.2 of ethylenically unsaturated groups per 100g of the binder on a dry basis.
 23. The sheet or film of claim 14,wherein the hydroxylalkyl (meth)acrylic groups are C₁-C₄hydroxalkyl(meth)acrylates.
 24. The sheet or film of claim 14, whereinthe outer layer is a clear coat layer.
 25. The sheet or film of claim14, wherein the outer layer is UV curable.
 26. The sheet or film ofclaim 14, wherein the radiation-curable composition comprises a majorportion of the binder.
 27. A cross-linked sheet or film obtained byradiation curing the sheet or film of claim
 14. 28. A process forproducing the composite layered sheet of film according to claim 27,comprising: applying the outer layer on the at least one substrate layerand the coloring interlayer, to form a laminate having a substratelayer, a coloring layer, and an outer layer, and curing theradiation-curable composition with a high-energy light or electronbeams.
 29. The process according to claim 28, wherein the curing isradiation curing effected at a temperature above the T_(g) of theradiation-curable binder.
 30. The process according to claim 28, furthercomprising applying a protective layer on the outer layer.
 31. Theprocess according to claim 30, further comprising removing theprotective layer prior to the curing.
 32. The process according to claim30, wherein the protective layer is transparent to the wavelength rangeof the high-energy light or the electron beams, and wherein the curingtakes place through the protective layer.
 33. The process according toclaim 28, further comprising applying an adhesive layer to a surface ofthe substrate that is opposite to the surface upon which the outer layeris applied.
 34. A process for producing the radiation-curable compositelayered sheet of film according to claim 27, comprising coextruding orlaminating at least one substrate layer and at least one coloringinterlayer to form a laminate having a substrate layer and a coloringlayer, applying the outer layer to a composite comprising a substratelayer and a coloring interlayer, and curing the radiation-curablecomposition with high energy light or electron beams.
 35. The processaccording to claim 34, wherein the curing is radiation curing effectedat a temperature above the T_(g) of the radiation-curable binder. 36.The process according to claim 34, further comprising applying aprotective layer on the outer layer.
 37. The process according to claim34, further comprising applying an adhesive layer to a surface of thesubstrate that is opposite to the surface upon which the outer layer andcoloring layer is applied.
 38. The process according to claim 34,wherein the radiation-curable composition is applied to the composite bycasting, rolling, knife coating or spraying.
 39. A coated moldingobtainable by a process comprising coating the sheet or film of claim 14on a molding; and curing the outer layer of the coated sheet or film bymeans of radiation.